This application is a 371 of PCT/FR99/00085 submitted Jan. 18, 1999.
The present invention relates to the use as protective agent for keratinous fibres of poly(heterocyclic quaternary ammonium) polymers, to cosmetic compositions employing them and to hair treatment processes in which these polymers are used.
Provision has already been made to use polymers comprising quaternary ammonium groups as hair conditioning agents. Such compositions are disclosed in particular in the French patents of the Applicant Company Nos. 2,270,846, 2,307,271 and 2,413,907.
Cationic polymers exhibit a high affinity for keratinous fibres, such as the hair, due to the interaction of the cationic groups with the anionic groups of the individual hair.
The deposition of these polymers on the hair becomes easier as the latter becomes more sensitized and their affinity for the hair is often such that they withstand removal by shampooing or by brushing.
However, it has been found that, while the use of such cationic polymers exhibits numerous advantages in so far as they facilitate disentangling of the hair and as they confer qualities of liveliness and a glossy appearance thereon, due to their affinity for keratin, these polymers have a tendency to accumulate on the hair following repeated applications.
Cationic polymers comprising quaternary groups furthermore often exhibit the disadvantage of not being very compatible with anionic surface-active agents, which reduces the possibilities of use and requires them to be used in two-step treatments, before or after shampooing.
The Applicant Company has discovered that some poly(quaternary ammonium) polymers, which do not exhibit the abovementioned disadvantages, comprising at least unsaturated quaternary heterocycles, are particularly advantageous in hair treatment.
The Applicant Company has discovered in particular that the use of these polymers makes it possible to protect the hair both with regard to attacks due in particular to the sun, to bad weather or to perspiration and with regard to those resulting from hair treatment, such as, for example, bleachings, permanent waves or dyeings.
It has been found that keratinous fibres have a tendency to be rendered brittle when they are subjected to these treatments; the hair becomes dry, dull and rough, and difficult to disentangle and to style.
The protective agents of the invention are of use in particular in any cosmetic process comprising at least one stage during which the keratinous fibres are liable to be exposed to various attacks and thus make it possible to avoid the abovementioned disadvantages.
These protective agents can be applied to the keratinous fibres during, prior to or subsequent to this stage during which the keratinous fibres are subjected to attacks.
The protective agents of the present invention are preferably used in a process during which at least one application of an alkaline composition to the keratinous fibres takes place.
A subject-matter of the invention is thus the use as protective agent of heterocyclic polyquaternary polymers.
Another subject-matter of the invention is cosmetic compositions employing them and in particular compositions intended for permanent shaping of keratinous fibres, bleaching compositions and dyeing compositions, preferably oxidation dyeing compositions.
A further subject-matter of the invention is a hair treatment process employing these compositions.
Other subject-matters of the present application will emerge on reading the description and examples which follow.
The polymers used as protective agent for keratinous fibres are basically composed of repeat units of formula (I): 
in which:
A1xcfx81 and A2xcfx81, which are identical or different, denote:
a) an unsaturated quaternary heterocycle of formula (II): 
xe2x80x83in which:
E, G, L and J, which are identical or different, denote a carbon, oxygen, sulphur or nitrogen atom, at least one denoting a nitrogen atom;
E, G, L and J can be substituted, when one or more of these atoms denote a carbon atom, by one or more halogen atoms, hydroxyl, nitro, cyano, mercapto or carboxyl groups, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl or acetyloxy group, a substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl group, or xe2x80x94NHRN groups in which RN denotes an acetyl or ureido group.
When E, G, L or J denotes a third nitrogen atom, the latter can be substituted by a hydrogen or an alkyl, monohydroxyalkyl, polyhydroxyalkyl, substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl radical.
The substituents of two of the E, G, L and J atoms can also form, jointly with the atoms to which they are attached, a substituted or unsubstituted 5- to 7-membered aromatic ring; or
b) a quaternary ammonium of formula (III) 
xe2x80x83in which:
R1 and R2, which are identical or different, denote a carboxyl group, an alkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl or acetyloxy group, a substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl group or an xe2x80x94NHRN group in which RN denotes an acetyl or ureido group;
R1 and R2 can also form, jointly with the nitrogen atom to which they are attached, a saturated 5- to 7-membered carbonaceous ring;
and in which at least one of the A1xcfx81 or A2xcfx81 groups denotes an unsaturated quaternary heterocycle of formula (II).
B1 and B2, which are identical or different, denote a hydrocarbonaceous group which can comprise, bonded to or inserted in the main chain, one or more substituted or unsubstituted aromatic rings, one or more oxygen, sulphur or nitrogen atoms, or one or more xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SO3H, amino, alkylamino, hydroxyl, quaternary ammonium or ureido groups.
X"sgr" represents an anion derived from an organic or inorganic acid.
The polymers of the present invention have a mass-average molecular weight preferably of between 1000 and 20,000, measured by gel permeation chromatography using polyethylene glycol as reference.
In the context of the present invention:
The halogen atoms preferably denote a fluorine, chlorine, bromine or iodine atom.
The alkyl, monohydroxyalkyl or polyhydroxyalkyl radicals and the hydrocarbonaceous groups can be linear or branched.
The alkyl groups denote in particular groups of 1 to 20 carbon atoms, such as, for example, the methyl, ethyl, propyl, isopropyl, n-propyl, butyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and pentadecyl groups. The alkyl groups preferably denote a group of 1 to 6 carbon atoms.
Mention may be made, among the hydrocarbonaceous groups, of polymethylene groups of 1 to 20 carbon atoms.
The hydrocarbonaceous groups preferably denote polymethylene groups of 2 to 8 carbon atoms.
The hydrocarbonaceous groups can comprise, bonded to or inserted in the main chain, one or more aromatic rings, one or more oxygen, sulphur or nitrogen atoms, or one or more xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SO3H, amino, alkylamino, hydroxyl, quaternary ammonium or ureido groups.
Mention may in particular be made, among the monohydroxyalkyl groups, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
Mention may be made, among the Apolyhydroxyalkyl radicals, of, for example, dihydroxyethyl, dihydroxypropyl, trihydroxypropyl and dihydroxybutyl radicals.
The thioalkyl radicals denote an xe2x80x94Rxe2x80x94SH group, R representing an alkyl group as defined above.
The cyanoalkyl radicals denote an xe2x80x94Rxe2x80x94Cxe2x95x90N group, R representing an alkyl group as defined above.
The alkoxy groups denote an xe2x80x94Oxe2x80x94R group, R representing an alkyl group as defined above.
The acyl groups denote an xe2x80x94OCxe2x80x94R group, R representing an alkyl group as defined above.
The acetyloxy groups denote an xe2x80x94Oxe2x80x94COxe2x80x94R group, R representing an alkyl group as defined above.
Mention may in particular be made, among the cycloalkyl radicals, of cyclohexyl and cyclopentyl.
Mention may in particular be made, among the aryl radicals, of phenyl or naphthyl groups.
Mention may in particular be made, among the alkylaryl groups, of the benzyl, phenethyl or naphthylmethyl group.
Mention may be made, among the 5- to 7-membered aromatic rings, of, for example, the abovementioned aryl or alkylaryl rings. The preferred aromatic rings are phenyl, pyrimidine, pyridine, pyrrole and pyrazole rings.
In the context of the present invention, the cycloalkyl radicals and the aromatic rings can be substituted by a halogen atom or a hydroxyl, amino or C1-C6 alkyl or hydroxyalkyl group.
X"sgr" represents in particular an anion derived from a halogen, such as chlorine, bromine, fluorine or iodine, an anion derived from inorganic acids, such as phosphoric acid or sulphuric acid, or an anion derived from an organic sulphonic or carboxylic acid, in particular an alkanoic acid having from 1 to 12 carbon atoms, such as acetic acid, a phenylalkanoic acid, such as phenylacetic acid, benzoic acid, citric acid or para-toluenesulphonic acid. X"sgr" preferably represents an anion derived from a halide and more preferably X"sgr" represents a chloride or bromide anion.
A1 and/or A2 preferably represents a heterocycle of formula (II) comprising 2 nitrogen atoms and 3 carbon atoms.
In a preferred embodiment of the present invention, at least one of the A1l or A2xcfx81 groups denotes a quaternary imidazole group of formula (IV): 
in which:
R3, R4 and R5, which are identical or different, denote a hydrogen or halogen atom, a hydroxyl, nitro, cyano, mercapto or carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl or acetyloxy group, a cycloalkyl, aryl or alkylaryl group or an xe2x80x94NHRN group in which RN denotes an acetyl or ureido group; the R4 and R5 radicals can also form, jointly with the atoms to which they are attached, a 5- to 7-membered aromatic ring.
In another embodiment of the present invention, at least one of the A1xcfx81 or A2xcfx81 groups denotes a quaternary pyrazole group of formula (V): 
in which:
R6, R7 and R8, which are identical or different, denote a hydrogen or halogen atom, a hydroxyl, nitro, cyano, mercapto or carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl or acetyloxy group, a cycloalkyl, aryl or alkylaryl group or an xe2x80x94NHRN group in which RN denotes an acetyl or ureido group;
two of the R6, R7 or R8 radicals can also form, jointly with the atoms to which they are attached, a 5- to 7-membered aromatic ring.
In another preferred embodiment of the present invention, the A1xcfx81 and A2xcfx81 groups simultaneously denote a quaternary imidazole group of formula (IV) in which R3, R4 and R5, which are identical or different, denote a hydrogen atom, a hydroxyl, nitro, cyano, mercapto or carboxyl group or an alkyl, monohydroxyalkyl or polyhydroxyalkyl group; the R4 and R5 radicals can also form, jointly with the atoms to which they are attached, a 5- to 7-membered aromatic ring.
In another particularly preferred form of the present invention, the A1xcfx81 and A2xcfx81 groups simultaneously denote a quaternary imidazole group of formula (IV) in which R3, R4 and R5, which are identical or different, denote a hydrogen atom or a C1 to C6 alkyl group and the R4 and R5 radicals can form, jointly with the atoms to which they are attached, a phenyl ring.
In another preferred embodiment of the present invention, A1xcfx81 represents a quaternary ammonium of formula (III) in which R1 and R2, which are identical or different, denote a hydrogen atom or a C1 to C6 alkyl group or form, jointly with the nitrogen, a 6-membered group and A2xcfx81 denotes a quaternary imidazole group of formula (IV) in which R3, R4 and R5, which are identical or different, denote a hydrogen atom or a C1-C6 alkyl.
In a preferred embodiment of the invention, at least one of the B1 or B2 groups denotes a group of formula (VI)
xe2x80x94(CH2)nxe2x80x94COxe2x80x94Axe2x80x94OCxe2x80x94(CH2)nxe2x80x94xe2x80x83xe2x80x83(VI)
in which:
n denotes an integer from 1 to 10 and preferably an integer from 1 to 6,
A denotes:
(a) a glycol residue of formula:
xe2x80x94Oxe2x80x94Zxe2x80x94Oxe2x80x94
in which Z denotes a hydrocarbonaceous group or a group corresponding to the formulae: 
in which x and y denote any number from 1 to 4; or
(b) a bis(secondary amine) residue, such as a piperazine derivative; or
(c) a bis(primary amine) residue of formula:
xe2x80x94NHxe2x80x94Yxe2x80x94NHxe2x80x94
in which Y denotes a hydrocarbonaceous group or a radical
xe2x80x94(CH2)2xe2x80x94Sxe2x80x94Sxe2x80x94(CH2)2xe2x80x94; or
(d) a ureylene group, that is to say a group of formula xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94.
In a preferred embodiment, B1 and B2, which are identical or different, denote a polymethylene group which can comprise one or more oxygen atoms or one or more aromatic rings.
In a particularly preferred embodiment, B1 and B2, which are identical or different, denote a group of formula:
xe2x80x94(CH2)nxe2x80x94;
n denoting an integer from 1 to 6, or 
xe2x80x83or
xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94.
Preferably, in the abovementioned polymers, X"sgr" represents a halide.
Some polymers used hereinabove are novel per se and constitute, as such, another subject-matter of the invention.
One family of these novel polymers is composed of the polymers based on repeat units of formula (VII): 
in which:
A1xcfx81 denotes an unsaturated quaternary heterocycle of formula (II) as defined hereinabove and A2xcfx81 denotes a quaternary ammonium of formula (III); B1, B2, X"sgr" and the formulae (II) and (III) being as defined hereinabove and at least one of the B1 or B2 groups being other than xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94.
In the formula (VII), the unsaturated quaternary heterocycles of formula (II), the quaternary imidazole groups of formula (IV) as defined hereinabove and the quaternary pyrazole groups of formula (V) as defined hereinabove are preferred.
One family of novel polymers is basically composed of repeat units of formula (VIII): 
in which
A1xcfx81 denotes a quaternary imidazole group of formula (IV) as defined hereinabove and A2xcfx81 denotes a quaternary pyrazole group of formula (V) as defined hereinabove; B1, B2 and X"sgr" being as defined hereinabove.
Another family of novel polymers is represented by the polymers basically composed of repeat units of formula (IX): 
in which A1xcfx81 is as defined in the formula (I) and in which A2xcfx81 denotes a quaternary imidazole group of formula (IV) in which R4 and R5, which are identical or different, are as defined in the abovementioned formula (IV) and R3 denotes a cycloalkyl, aryl or alkylaryl group and preferably a phenyl group; B1, B2 and X"sgr" being as defined hereinabove.
Among the novel compounds (IX), those in which A1xcfx81 denotes a quaternary imidazole of formula (IV), and more particularly when the R3 group of (IV) denotes a phenyl, are particularly preferred.
Among the preferred novel compounds (VII), (VIII) and (IX), B1 and/or B2 preferably denotes a group of formula (VI):
xe2x80x94(CH2)nxe2x80x94COxe2x80x94Axe2x80x94OCxe2x80x94(CH2)nxe2x80x94xe2x80x83xe2x80x83(VI)
in which:
n denotes an integer from 1 to 10;
A denotes:
(a) a glycol residue of formula:
xe2x80x94Oxe2x80x94Zxe2x80x94Oxe2x80x94
in which Z denotes a hydrocarbonaceous group or a group corresponding to the formulae: 
which x and y denote any number from 1 to 4; or
(b) a bis(secondary amine) residue; or
(c) a bis(primary amine) residue of formula:
xe2x80x94NHxe2x80x94Yxe2x80x94NHxe2x80x94
in which Y denotes a hydrocarbonaceous group or the radical
xe2x80x94(CH2)2xe2x80x94Sxe2x80x94Sxe2x80x94(CH2)2xe2x80x94; or
(d) a ureylene group,
and more particularly xe2x80x94(CH2)nxe2x80x94, n denoting an integer from 1 to 6; or
xe2x80x83xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94
and at least one of the B1 or B2 groups being other than xe2x80x94CH2xe2x80x94CROHxe2x80x94CH2xe2x80x94, with R=H or alkyl, and the B1 and B2 groups being other than the group: 
The synthesis of the compounds of the present invention is carried out in two stages. The first stage consists in synthesizing the diamine and then the second stage consists of the quaternization of the diamine in the presence of a dihalide or of a disulphonate.
The synthesis of a diamine is carried out by the reaction of the corresponding diazole with a dihalide or a disulphonate in a solvent, in the presence of a base, at a temperature between room temperature and the reflux temperature.
These solvents can be water, aromatic solvents, such as benzene or toluene, dimethyl sulphoxide, tetrahydrofuran or dimethylformamide.
These solvents can also be used as a mixture.
The bases can be hydroxides, such as sodium hydroxide or potassium hydroxide, or amides, carbonates or hydrides.
This synthesis can also take place under phase transfer conditions by the addition of a phase transfer agent.
Syntheses are described in particular in the documents J. Elguero et al., Journal of Heterocyclic Chemistry, 25, 771-782 (1988), Yin-hung So, Macromolecules, 25, 516-520 (1992) and R. G. Xie et al., Chinese Chemical Letters, 7, 321-324 (1996).
The quaternization with a dihalide or a disulphonate is carried out in a solvent at a temperature between room temperature and the reflux temperature. The solvents can be chosen from water, alcohols, aromatic solvents, such as benzene or toluene, dimethyl sulphoxide, tetrahydrofuran or dimethylformamide. These solvents can also be used as a mixture. They are preferably chosen from water, alcohols and aqueous/alcoholic mixtures.
The unsaturated heterocyclic quaternary polymers used in accordance with the invention for the protection of the hair are used in particular in compositions used for the permanent deformation of the hair, for dyeing or for bleaching which constitute another subject-matter of the invention.
The commonest technique for obtaining a permanent deformation of the hair consists, in a first step, in applying a composition comprising a reducing agent to the keratinous fibres and then, in a second step, in applying an oxidizing composition to the hair, which has been placed under tension beforehand with curlers or other means, so as to ultimately give the hair the desired shape.
The protective agents of the present invention can be present in the reducing and/or oxidizing composition.
The reducing compositions in accordance with the invention comprise, in a medium appropriate for the permanent deformation of the hair, at least one reducing agent capable of breaking the disulphide bonds (xe2x80x94Sxe2x80x94Sxe2x80x94) in the individual hairs and at least one unsaturated heterocyclic quaternary polymer as defined hereinabove.
The reducing agents are generally chosen from sulphites, bisulphites or thiols.
Mention may be made, among the preferred reducing agents, of cysteine, cysteamine and their derivatives, such as their cosmetically acceptable salts, for example the hydrochlorides, hydrobromides, citrates, acetates or sulphates, or thiolactic acid, thioglycolic acid and their esters, in particular glyceryl thioglycolate.
The reducing agents are present in proportions which are sufficient to reduce the disulphide bonds of the keratin, preferably of between 1 and 25% and in particular between 1 and 10% by weight.
The protective agents of the present invention can be present in proportions of between 0.01% and 10% by weight of the reducing composition and preferably between 1% and 5%.
The pH of the reducing compositions is adjusted so as to obtain a pH of between 6.5 and 11.5.
The alkaline agents are preferably chosen from monoethanolamine, diethanolamine, triethanolamine, isopropylamine, 2-methylamino-1-propanol, 1,3-propanediamine, an alkali metal or ammonium carbonate or bicarbonate, aqueous ammonia, an organic carbonate, such as guanidine carbonate, or an alkaline hydroxide, used alone or as a mixture.
This reducing composition can also comprise nonionic, anionic, cationic or amphoteric surface-active agents commonly used in such compositions. Mention may be made, among these, of alkyl sulphates, alkylbenzenesulphonates, alkyl ether sulphates, alkylsulphonates, quaternary ammonium salts, alkyl betaines, oxyethylenated alkylphenols, alkylpolyglucosides, fatty acid alkanolamides, oxyethylenated fatty acid esters and nonionic surfactants from the family of the hydroxypropyl ethers.
These surface-active agents are generally used in maximum proportions of 30% and preferably of between 0.5 and 10% by weight with respect to the total weight of the composition.
These compositions can also comprise thickening agents, such as guar gum, tara gum or spruce flour.
These compositions can also comprise treating agents, such as volatile or non-volatile, linear or cyclic silicones or their mixtures. Mention may be made, among the silicones, of polydimethylsiloxanes, quaternized polyorganosiloxanes as disclosed in FR-A-2,535,730, polyorganosiloxanes comprising an aminoalkyl group which are modified by alkoxycarbonylalkyl groups as disclosed in the U.S. Pat. No. 4,749,732, polyorganosiloxanes, such as polydimethylsiloxane-polyoxyalkyl copolymers, such as dimethicone copolyol, a polydimethylsiloxane comprising end stearoxy groups (stearoxydimethicone), a polydimethylsiloxane-dialkylammonium acetate copolymer or a polydimethylsiloxane-poly(alkyl betaine) copolymer disclosed in GB-A-2,197,352, polysiloxanes organomodified by mercapto or mercaptoalkyl groups as disclosed in FR-B-1,530,369 and EP-A-0,295,780, and silanes, such as stearoxytrimethylsilane.
Other ingredients which can be used in the reducing compositions comprising the protective agents of the invention are chosen from waxes, polymers chosen from cosmetically acceptable anionic, cationic (other than those of the invention), nonionic or amphoteric polymers, swelling and penetrating agents which make it possible to reinforce the effectiveness of the reducing agent, such as dimethylisosorbitol, urea and its derivatives, pyrrolidone, n-alkylpyrrolidones, thiamorpholinone, alkylene glycol or dialkylene glycol alkyl ethers, such as, for example, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether, C3-C6 alkanediols, such as 1,2-propanediol, or 2-imidazolidinone, and other compounds, such as fatty alcohols, lanolin derivatives, ceramides, in particular ceramides themselves, glycoceramides or pseudoceramides disclosed in particular in FR-A-95 12399 and in Downing, Journal of Lipid Research, Vol. 35, p. 2060, 1994, or in FR-A-2,673,179, EP-A-0,227,994, WO-94/07844 and WO-92/05764, active ingredients, such as pantothenic acid or panthenol, agents for combating hair loss, antidandruff agents, suspending agents, sequestering agents, opacifying agents, dyes, silicone-comprising or non-silicone-comprising sunscreens, fragrances and preservatives.
The protective agents defined hereinabove can also be present in oxidizing compositions used during the permanent shaping of keratinous fibres. Another subject-matter of the invention is thus an oxidizing composition for the permanent shaping of keratinous fibres comprising, in a medium appropriate for permanent waving, an oxidizing agent and a polymer as defined hereinabove.
The oxidizing agents can be chosen from aqueous hydrogen peroxide solution, urea hydrogen peroxide, bromates, such as alkaline bromates, persalts or a mixture of alkaline bromates and of a persalt.
When the oxidizing agent is composed of aqueous hydrogen peroxide solution, it is present in proportions of between 1 and 10 volumes and preferably of the order of 8 volumes.
When bromates are used, the concentration of alkaline bromates is from 1 to 12% and that of persalts from 0.1 to 15% by weight with respect to the total weight of the oxidizing composition.
The protective agents of the present invention can be present in proportions of between 0.01% and 10% by weight of the oxidizing composition and preferably between 1% and 5% by weight.
The pH of these compositions is usually between 2 and 9 and preferably between 3 and 8; it is preferably acidic.
When aqueous hydrogen peroxide solution is used, it can be stabilized with phenacetin, acetaniline, mono- and trisodium phosphates or 8-hydroxyquinoline sulphates.
Another subject-matter of the invention is a process for the permanent shaping of keratinous fibres and in particular of the hair, essentially characterized in that:
a composition which reduces keratin is applied to the keratinous fibres, preferably wet keratinous fibres, the reducing composition being applied to the shaped fibres,
after a setting time sufficient to reduce the keratin, an oxidizing composition is applied,
after a setting time sufficient to fix the fibres, shaped and reduced in the first stage, in a permanent shape, rinsing is carried out, preferably with water; the reducing composition and/or the oxidizing composition being as defined hereinabove.
The hair is shaped by various means, such as rollers, clips, hair grips or simply by hand.
Another subject-matter of the present invention is a composition for the direct dyeing of keratinous fibres and in particular of human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing, at least one polymer as defined hereinabove and at least one direct dye.
Mention may be made, among direct dyes conventionally used, of nitrobenzene dyes, such as nitrophenylenediamines, nitrodiphenylamines, nitroanilines, nitrophenol ethers or nitrophenols, nitropyridines, anthraquinone, mono- or diazo, triarylmethane, azine, acridine and xanthene dyes or metalliferous dyes.
The direct dyes more particularly preferred according to the invention are chosen from the following:
i) nitrobenzene dyes of following formula (A): 
xe2x80x83in which
R3 denotes an NH2 radical, an amino radical monosubstituted by an alkyl, monohydroxyalkyl, polyhydroxyalkyl or aminoalkyl radical or an amino radical disubstituted by identical or different alkyl, monohydroxyalkyl, polyhydroxyalkyl or aminoalkyl radicals,
R4 denotes hydrogen, hydroxyl, alcoxy, monohydroxyalkyloxy, polyhydroxyalkyloxy or the same meanings denoted hereinabove for R3, with the exception of the disubstituted amino radical,
R5 denotes hydrogen, alkyl, nitro or halogen,
ii) anthraquinone dyes of following formula B: 
xe2x80x83in which
R6 denotes hydrogen or a monohydroxyalkyl or polyhydroxyalkyl radical,
R7 denotes hydrogen or an alkyl or alkoxy radical,
R8 denotes hydrogen or a hydroxyl, amino, monohydroxyalkylamino or polyhydroxyalkylamino radical,
R9 and R10, which are identical or different, are hydrogen, hydroxyl or amino,
iii) azo dyes of following formula (C): 
xe2x80x83in which:
R11 denotes a nitro or amino radical or an amino radical mono- or disubstituted by alkyls,
R12 denotes hydrogen or an alkyl radical,
R13 denotes an amino radical or an amino radical mono- or disubstituted by monohydroxyalkyls, it being understood that the alkyl and alkoxy radicals mentioned hereinabove in the formulae (A), (B) and (C) are C1-C4 radicals and that they can be linear or branched, and the cosmetically acceptable salts of all these compounds.
The term xe2x80x9cC1-C4xe2x80x9d is understood to mean in particular the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals.
The term xe2x80x9ccosmetically acceptable saltsxe2x80x9d denotes more particularly the hydrochlorides, hydrobromides and sulphates.
More advantageously still, according to the present invention, it is preferable to employ the following direct dyes:
1-amino-2-nitro-4-Nxe2x80x94(xcex2-hydroxyethyl)amino-5-methylbenzene,
1,4,5,8-tetraaminoanthraquinone,
1,4-bis-N,Nxe2x80x2-[(xcex2, xcex3-dihydroxypropyl)amino]-anthraquinone,
1,4,4-N-tris(xcex2-hydroxyethyl)-1,4-diamino-2-nitrobenzene,
1-N-(xcex2-hydroxyethyl)amino-2-nitro-4-aminobenzene,
1-hydroxy-3-nitro-4-aminobenzene,
1-hydroxy-3-nitro-4-N-(xcex2-hydroxyethyl)aminobenzene,
1-(xcex2-hydroxyethyloxy)-3-methylamino-4-nitrobenzene,
1-methylamino-2-nitro-5-(xcex2, xcex3-dihydroxypropyloxy)benzene,
1-N-(xcex2-aminoethyl)amino-2-nitro-4-(xcex2-hydroxyethyloxy)benzene,
4-[N-ethyl-N-(xcex2-hydroxyethyl)amino]-1-N-(xcex2-hydroxyethyl)amino-2-nitrobenzene,
1-(4xe2x80x2-aminodiphenylazo)-2-methyl-4-N-bis(xcex2-hydroxyethyl)aminobenzene,
1-methoxy-3-N-(xcex2-aminoethyl)amino-4-nitrobenzene,
1-amino-2-nitro-4-N-(xcex2-hydroxyethyl)aminobenzene,
1-amino-2-nitro-4-N-bis(xcex2-hydroxyethyl)aminobenzene,
1,4-N-bis(xcex2-hydroxyethyl)amino-5-nitrobenzene,
1,4-diaminoanthraquinone,
and their cosmetically acceptable salts.
Other preferred cationic dyes are those of Arianor type (Basic Brown 17, Basic Brown 16, Basic Yellow 57, Basic Blue 99) and the cationic dyes disclosed in the Ciba Patents WO 95/01772, WO 95/15144 and EP 714,954.
The direct dyes, in the base or salified form, are generally present in the dyeing composition according to the invention in proportions which can range from approximately 0.001 to approximately 10% and preferably from approximately 0.05 to approximately 5% by weight with respect to the total weight of the composition.
The present invention also relates to a composition for the oxidation dyeing of keratinous fibres and in particular of human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing, at least one polymer as defined hereinabove and at least one oxidation dye precursor and/or melanin precursors.
The oxidation dye precursors can be chosen in particular from para-phenylenediamines, para-aminophenols, ortho-phenylenediamines and heterocyclic bases, such as, for example, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives, indoles or indolines, and their acid addition salts.
These compositions can also include couplers, which can be chosen in particular from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers, such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives or pyridine, pyrimidine and pyrazole derivatives, and their addition salts with an acid.
Generally, the addition salts with an acid which can be used in the context of dyeing compositions are chosen in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The medium appropriate for direct or oxidation dyeing (or support) is generally composed of water or of a mixture of water and of at least one organic solvent, in order to dissolve the compounds which would be insufficiently soluble in water.
Mention may be made, as organic solvent, of, for example, lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether; and aromatic alcohols, such as benzyl alcohol or phenoxyethanol, the analogous products and their mixtures.
When they are present, the oxidation base or bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition.
When they are present, the coupler or couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition.
The polymers of the invention preferably represent from 0.01 to 10% by weight approximately of the total weight of the direct or oxidation dyeing composition and preferably from 0.1 to 5%.
The solvents can be present in proportions preferably of between 1 and 40% by weight approximately with respect to the total weight of the dyeing composition and more preferably still between 5 and 30% by weight approximately.
The pH of the dyeing compositions is generally between 3 and 12 approximately and preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in the dyeing of keratinous fibres.
Mention may be made, among the acidifying agents, by way of example, of inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, or sulphonic acids.
Mention may be made, among the basifying agents, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines and their derivatives, sodium hydroxide, potassium hydroxide and the compounds of following formula: 
in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C6 alkyl radical and R4, R5, R6 and R7 which are identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
The dyeing compositions comprising a protective agent can also include various adjuvants conventionally used in hair dyeing compositions.
The oxidizing compositions used in oxidation dyeing which constitute another subject-matter of the invention can also comprise an unsaturated heterocyclic quaternary polymer as defined hereinabove and at least one oxidizing agent.
These oxidizing agents can be chosen in particular from hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates, persalts, such as perborates and persulphates, and enzymes, such as peroxidases and two-electron oxidoreductases.
Another subject-matter of the invention is a hair dyeing process, characterized in that a composition as defined hereinabove comprising the protective agent in accordance with the invention, optionally with an oxidizing composition in the case of oxidation dyeing, is applied to the hair in an amount sufficient to dye the hair. In the case of oxidation dyeing, only the composition comprising the dye precursors or the oxidizing composition can include a polymer according to the invention. The composition is allowed to act for a time of between 5 and 45 minutes approximately and then the hair is rinsed.
For direct dyeing, a composition as defined hereinabove comprising at least one direct dye is applied to the hair in an amount sufficient to produce a colouring and is allowed to act for a time of between 10 and 60 min approximately. The hair is then rinsed.
It is also possible to carry out direct dyeings without rinsing.
Another subject-matter of the present invention is a bleaching composition comprising, in a medium appropriate for bleaching, an agent for bleaching the hair and a protective agent as defined hereinabove.
Use is made, in bleaching the hair, of bleaching agents known per se, such as hydrogen peroxide, persulphates, sodium percarbonate, or perborates.
To bleach the hair, a bleaching composition as defined hereinabove is applied to the hair in an amount and for a time sufficient to bleach the hair. The hair is subsequently rinsed.
The invention also relates to compositions intended for the cosmetic treatment of the hair comprising a novel heterocyclic quaternary polymer as defined in the formulae VII, VIII and IX.
The examples which follow are intended to illustrate the invention.
Tables 1 and 2 hereinbelow are intended to illustrate the preparation of polymers used according to the invention.
The information relating to the structure of the compound of the polymer of formula (I) is successively shown in these tables.
a) Synthesis of the Diamine 1,1xe2x80x2-(1,3-Propanediyl)bisimidazole
35.4 g (0.52 mol) of imidazole, a solution of 100 g (2.5 mol) of sodium hydroxide in 100 ml of water, 5.15 g of tetrabutylammonium bromide and 52.49 g (0.26 mol) of 1,3-dibromopropane in solution in 240 ml of toluene are introduced into a reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser. This mixture is brought to reflux for 32 hours. After cooling, 150 ml of water are added to the mixture. The reaction mixture then exhibits three liquid phases. After separating by settling, the intermediate phase, which is insoluble in the usual organic solvents, is recovered and is distilled. 27.5 g of slightly yellow transparent oil are thus separated.
The results obtained by DMSO proton NMR are as follows:
xcex4 2.22 (m, 2H), xcex4 3.92 (t, 4H), xcex4 6.91 (m, 2H), xcex4 7.17 (m, 2H), xcex4 7.61 (m, 2H)
b) Synthesis of the Polymer
A mixture of 17.6 g (0.1 mol) of the diamine obtained hereinabove, 100 ml of methanol and 20.2 g (0.1 mol) of 1,3-dibromopropane is brought to reflux for 10 hours. After evaporating the solvent, the residue is ground in 300 ml of isopropyl ether until a powder is obtained, which powder is filtered off and dried under vacuum in the presence of phosphorus pentoxide. 34.6 g of a hydroscopic beige powder are thus obtained with a yield of 91.5%. Quantitative determination of the bromides by AgNO3: 40.4% (theory: 42.3%)
a) Synthesis of the Diamine 1,1xe2x80x2-(1,4-Butanediyl)bisimidazole
35.4 g (0.52 mol) of imidazole, a solution of 100 g (2.5 mol) of sodium hydroxide in 100 ml of water, 5.15 g of tetrabutylammonium bromide and 54 g (0.26 mol) of 1,4-dibromobutane in solution in 240 ml of toluene are introduced into a reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser. This mixture is brought to reflux for 6 hours. After cooling, the expected diamine crystallizes and is filtered off and the cake obtained is washed with 100 ml of toluene and then with 2 times 50 ml of ice-cold water. The product, thus washed, is recrystallized from 200 ml of water. After drying, 44 g of light beige powder are obtained (yield: 89%). An analysis by DMSO proton NMR gave the following results:
xcex4 1.61-1.68 (m, 4H), xcex4 3.96-4.02 (m, 4H), xcex4 6.91 (m, 2H), xcex4 7.17 (m, 2H), xcex4 7.64 (m, 2H)
b) Synthesis of the Polymer
A mixture composed of 24.73 g (0.13 mol) of the diamine obtained hereinabove, 210 ml of methanol and 26.25 g (0.13 mol) of 1,3-dibromopropane is brought to reflux for 56 hours. After evaporating the solvent, the residue is ground in 300 ml of isopropyl ether until a powder is obtained, which powder is filtered off and dried under vacuum in the presence of phosphorus pentoxide. The beige powder obtained (39.9 g; yield: 100%) is hygroscopic. Quantitative determination of the bromides by AgNO3: 38% (theory: 40.7%).
a) Synthesis of the Diamine 1,1xe2x80x2-(1,4-butanediyl)bisbenzimidazole
12.95 g (0.06 mol) of 1,4-dibromobutane are added dropwise at room temperature to a mixture of 31.4 g (0.78 mol) of ground potassium hydroxide, 14 g (0.12 mol) of benzimidazole and 200 ml of acetone and stirring is maintained at this temperature for 8 hours; the precipitate formed is then filtered off and is recrystallized directly from 50 ml of ethanol. 9.7 g of white powder are thus obtained with a melting point at 175xc2x0 C.
CDCl3 proton NMR analysis gave the following results: xcex4 1.87-1.92 (m, 4H), xcex4 4.1-4.16 (m, 4H), xcex4 7.24-7.3 (m, 6H), xcex4 7.77-7.84 (m, 4H).
b) Synthesis of the Polymer
A mixture of 7.31 g (0.025 mol) of 1,1xe2x80x2-(1,4-butanediyl)bisbenzimidazole, 50 ml of methanol and 5.05 g (0.025 mol) of 1,3-dibromopropane is brought to reflux for 40 hours. The reaction mixture is concentrated and then the residue is taken up in isopropyl ether; after filtering and drying, 12.3 g of white powder are obtained; % Br 31.65 (theory 32.3%).
A mixture of 20.37 g (0.1 mol) of 1,1xe2x80x2-(1,4-butanediyl)bisimidazole comprising 6.6% of water, 25 ml of water and 26.4 g (0.1 mol) of xcex1, xcex1xe2x80x2-dibromo-para-xylene is brought to 110xc2x0 C. for 5 hours in a hermetically sealed reactor. Quantitative determination by silver nitrate of a test sample shows that 98.3% of the bromides are in the ionic form after reacting for 5 h. The solution is adjusted to 50% of active material by taking into account the level of bromides. Quantitative determination of the bromides by AgNO3: 33.9% (theory: 35.2%) on a dry basis.
A mixture of 40.73 g (0.2 mol) of 1,1xe2x80x2-(1,4-butanediyl)bisimidazole comprising 6.6% of water, 100 ml of water and 38.6 g (0.2 mol) of 97% 1,2-bis(2-chloroethoxy)ethane (Aldrich) is brought to reflux for 8 hours. Quantitative determination by silver nitrate of a test sample shows that 97.8% of the chlorides are in the ionic form after reacting for 8 hours. The reaction mixture is concentrated slightly under vacuum in the presence of vegetable charcoal, the charcoal is filtered off and then the solution is adjusted to 50% of active material by taking into account the level of chlorides. 127 g of slightly amber solution are obtained.
Quantitative determination of the chlorides by AgNO3: 18.5% (theory: 18.8%) on a dry basis.
A mixture of 5.26 g at 95% (0.02 mol) of 1,1xe2x80x2-(1,2-bis(ethoxy)ethanediyl)bisimidazole, 10 ml of water and 3.74 g (0.02 mol) of 97% 1,2-bis(2-chloroethoxy)ethane (Aldrich) is brought to reflux for 21 hours. Quantitative determination by silver nitrate of a test sample shows that 96% of the chlorides are in the ionic form after reacting for 21 hours. The solution is then adjusted to 50% of active material by taking into account the level of chlorides. 15.5 g of light yellow solution are obtained.
Quantitative determination of the chlorides by AgNO3 in the light yellow solution: 2.28 meq/g.
A mixture of 3.95 g (0.015 mol) of 1,1xe2x80x2-(1,2-bis(ethoxy)ethanediyl)bisimidazole, 10 ml of water and 3.96 g (0.015 mol) of xcex1,xcex1xe2x80x2-dibromo-para-xylene is brought to reflux for 5 hours. Quantitative determination by silver nitrate of a test sample shows that 100% of the bromides are in the ionic form after reacting for 5 hours. The solution is filtered, is concentrated slightly under vacuum and is then adjusted to 50% of active material by taking into account the level of bromides. 14.8 g of amber-yellow solution are obtained.
Quantitative determination of the bromides by AgNO3: 1.94 meq/g of solution.
A mixture of 2.38 g (0.01 mol) of 1,1xe2x80x2-(xcex1, xcex1xe2x80x2-para-xylene)bisimidazole, 9 ml of water and 2.6 g (0.01 mol) of xcex1, xcex1xe2x80x2-dibromo-para-xylene is brought to reflux for 10 hours. Quantitative determination by silver nitrate of a test sample shows that 100% of the bromides are in the ionic form after reacting for 10 hours. The reaction mixture is concentrated and then the residue is taken up in 10 ml of methanol; the beige powder is filtered off. After drying under vacuum, 3.6 g of beige powder are obtained.
A mixture of 20.37 g (0.1 mol) of 1,1xe2x80x2-(1,4-butanediyl)bisimidazole comprising 6.6% of water, 50 ml of water and 17.5 g (0.1 mol) of xcex1, xcex1xe2x80x2-dichloro-para-xylene is brought to reflux for 5 hours. Quantitative determination by silver nitrate of a test sample shows that 97% of the chlorides are in the ionic form after reacting for 3 hours. The reaction mixture is left at 95xc2x0 C. for a further 2 hours. The solution is then adjusted to 50% of active material by taking into account the level of chlorides. 68.4 g of solution are obtained.
Quantitative determination of the chlorides by AgNO3: 18.8% (theory 19.4%) on a dry basis.
A mixture of 15.94 g (0.1 mol) of 96% N,N-dimethyl-1H-imidazole-1-propanamine, 40 ml of methanol and 15.5 g (0.1 mol) of 1,6-dichlorohexane is brought to reflux for 122 hours. Quantitative determination by silver nitrate of a test sample shows that 96% of the chlorides are in the ionic form after reacting for 122 hours. The solution is concentrated and the residue is dried under a vacuum of 0.1 mmHg. 30 g of very hygroscopic white powder are obtained.
Quantitative determination of the chlorides by AgNO3: 22.0% (theory: 22.9%).
A mixture of 2.51 g (0.0164 mol) of N,N-dimethyl-1H-imidazole-1-propanamine, 8.2 ml of methanol and 2.87 g (0.0164 mol) of xcex1, xcex1xe2x80x2-dichloro-para-xylene is brought to reflux for 5 hours. Quantitative determination by silver nitrate of a test sample shows that 94% of the chlorides are in the ionic form after reacting for 5 hours. The reaction mixture is left at 95xc2x0 C. for a further 2 hours. The solution is concentrated and the residue is dried under vacuum. 5.4 g of very hygroscopic white powder are obtained.
Quantitative determination of the chlorides by AgNO3: 19.5% (theory: 21.6%).
A mixture of 6.95 g (0.036 mol) of 1-(1H-piperidyl)-3-(1H-imidazolyl)propane, 15 ml of methanol and 6.3 g (0.036 mol) of xcex1, xcex1xe2x80x2-dichloro-para-xylene is brought to reflux for 6 hours. Quantitative determination by silver nitrate of a test sample shows that 100% of the chlorides are in the ionic form after reacting for 6 hours. The solution is concentrated and the residue is dried under vacuum. 13 g of hygroscopic slightly pinkish powder are obtained.
Quantitative determination of the chlorides by AgNO3: 18.3% (theory: 19.2%).
A mixture composed of 5.32 g (0.015 mol) of 96.6% 1,1xe2x80x2-(1,4-butanediyl)bis(2-phenylimidazole), 10 ml of water and 3.24 g (0.015 mol) of 1,4-dibromobutane is brought to reflux for 6 hours. Quantitative determination by silver nitrate of a test sample shows that 100% of the bromides are in the ionic form after reacting for 6 hours. The solution is filtered, is slightly concentrated under vacuum and is then adjusted to 50% of active material by taking into account the level of bromides. 8 g of light yellow solution are obtained.
Quantitative determination of the bromides by AgNO3: 1.79 meq/g of solution.
A mixture of 19.02 g (0.1 mol) of 1,1xe2x80x2-(1,4-butanediyl)bispyrazole, 40 ml of water and 17.5 g (0.1 mol) of xcex1, xcex1xe2x80x2-dichloro-para-xylene is brought to reflux for 3.5 hours. Quantitative determination by silver nitrate of a test sample shows that 99% of the chlorides are in the ionic form after reacting for 3.5 hours. Approximately 40 ml of water are added, the cloudy light material is filtered off and the solution is concentrated and adjusted to 50% of active material by taking into account the level of chlorides. 73 g of solution are obtained.
Quantitative determination of the chlorides by AgNO3: 17.96% (theory: 19.4%) on a dry basis.